WO2011149388A1 - Catalyseur à base de ruthénium de la polymérisation par métathèse de dicylcopentadiène (et variantes) et procédé de production de polycylcopentadiène (et variantes) - Google Patents

Catalyseur à base de ruthénium de la polymérisation par métathèse de dicylcopentadiène (et variantes) et procédé de production de polycylcopentadiène (et variantes) Download PDF

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Publication number
WO2011149388A1
WO2011149388A1 PCT/RU2011/000364 RU2011000364W WO2011149388A1 WO 2011149388 A1 WO2011149388 A1 WO 2011149388A1 RU 2011000364 W RU2011000364 W RU 2011000364W WO 2011149388 A1 WO2011149388 A1 WO 2011149388A1
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catalyst
ruthenium
imidazolidinylidene
benzylidene
bis
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PCT/RU2011/000364
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English (en)
Russian (ru)
Inventor
Василий Дмитриевич КОЛЕСНИК
Роман Витальевич АШИРОВ
Надежда Михайловна ЩЕГЛОВА
Роман Викторович ЯКИМОВ
Наталья Васильевна КИСЕЛЕВА
Мария Николаевна БОГОМОЛОВА
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Закрытое Акционерное Общество "Сибур Холдинг"
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Publication of WO2011149388A1 publication Critical patent/WO2011149388A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

  • the invention relates to organometallic chemistry, in particular to new complexes of transition metals of group 8, which are used as catalysts for the polymerization of cyclic olefins, in particular dicyclopentadiene (DCPD).
  • the invention can be applied in the field of catalysis, organic synthesis and organometallic chemistry.
  • the catalytic metathesis of olefins is a method that has recently become the subject of close attention, as a universal method for the formation of carbon-carbon bonds, which has been widely used in organic synthesis (R. N. Grubbs, Handbook of Metathesis, Volume 2 - Applications in Organic Synthesis Wiley-VCH, Weinheim, 2003) and Polymer Chemistry (RH Grubbs, Handbook of Metathesis, Volume 3 - Applications in Polymer Synthesis; Wiley-VCH, Weinheim, 2003).
  • the metathesis reaction was widespread with the advent of highly active molybdenum and ruthenium complexes with a specific structure (R. N. Grubbs, Handbook of Metathesis, Volume 1 - Catalyst Development; Wiley-VCH, Weinheim, 2003).
  • Grubbs catalysts of the first (Grl) and second (Grll) generations having the following structural formulas.
  • Polydicyclopentadiene (PDCPD) is a promising thermoset having a number of unique mechanical properties and high inertness, which makes it possible to produce impact-resistant products of large sizes and complex shapes from it.
  • the main disadvantages of PDCPD products obtained by the currently widely used Metton and Te1epe technologies are:
  • This catalyst has a long induction period during the metathesis polymerization, which allows for the controlled polymerization of dicyclopentadiene.
  • polymerization begins after 25 minutes at a temperature of 30 ° C and a molar ratio of monomer: catalyst of 30,000: 1.
  • the disadvantage of this catalyst is the need to use large amounts of catalyst relative to the monomer to achieve a high degree of polymerization.
  • the closest structural catalyst is the metathesis polymerization catalyst for ring-opening cyclic compounds (California Institute of Technology, Patent Application Publication US 2005261451 24.1 1.05), which is a ruthenium complex of the following structure:
  • the disadvantage of the prototype catalyst is a short induction period, which makes it difficult to control the onset and progress of the polymerization process.
  • the disadvantages of the prototype also include the need to use large quantities of expensive catalyst in relation to the monomer, which leads to an increase in the cost of the final product.
  • the objective of the invention is the creation of new effective catalysts for the controlled metathesis polymerization of dicyclopentadiene, as well as a method for producing polydicyclopentadiene.
  • a catalyst which is a complex ruthenium compound having 1, 3-bisaryl-2-imidazolidinylidene, two chlorine atoms and ortho-substituted benzylidene as ligands.
  • the aryl substituent in the 1, 3-bisaryl-2-imidazolidinylidene ligand is 2,6-dimethylphenyl
  • the substituent in the benzylidene ligand is the amino-substituted methyl group, where the dialkylamino, di (2-hydroxyethyl) amino, alkylphenylamino acts as an amine -groups, as well as cyclic amines, namely piperidine and morpholine.
  • the amino-containing substituent additionally coordinates to the ruthenium atom and forms a six-membered chelate cycle.
  • the catalyst has the following formula:
  • a catalyst is also proposed which is a complex compound of ruthenium having 1, 3-bisaryl-2-imidazolidinylidene, two chlorine atoms and ortho-substituted benzylidene as ligands.
  • SUBSTITUTE SHEET (RULE 26) is 2,4,6-trimethylphenyl, and the substituent in the benzylidene ligand is an alkyl phenylamino substituted methyl group.
  • the catalyst has the general formula:
  • the claimed catalysts are active during the metathesis polymerization of dicyclopentadiene, with a molar ratio of catalyst: monomer from 1: 70,000 to 1: 250,000, are readily soluble in the monomer, have high thermal stability, are insensitive to impurities contained in the monomer, and are stable during storage , and also are steady at contact with oxygen and air humidity.
  • an object of the invention is a method for producing polydicyclopentadiene, which consists in the fact that the polymerization of dicyclopentadiene is carried out in the presence of the proposed catalysts to control the induction period of the polymerization process, with a molar ratio of monomer-catalyst of from 70,000: 1 to 250,000: 1.
  • the technical result when implementing this method can be achieved by using [1, 3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (2- ( ⁇ [, ⁇ -bis (2-hydroxyethyl) amine k) benzylidene) ruthenium at a molar ratio of monomer-catalyst of 70,000: 1 to 250,000: 1 or [1, 3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene
  • Achievable technical result is expressed in a decrease in the consumption rate of the catalyst, which leads to a decrease in the cost of polydicyclopene gadiene, as well as the ability to control the time of the start of the polymerization process.
  • the synthesis is carried out in an argon atmosphere.
  • 3.60 g (4.5 mmol) of the first generation Grabbs catalyst bis (tricyclohexylphosphine) dichloro (3-methylbut-2-enylidene) ruthenium
  • 3-methylbut-2-enylidene ruthenium
  • 2, 86 g (7.2 mmol) of 1, 3-bis- (2,6-dimethylphenyl) -2-trichloromethylimidazolidine and 90 ml of dry toluene.
  • the reaction mass is stirred at a temperature of 75 ° C for 2 hours, after which 2.35 g (8.9 mmol) of o- (M, M-dimethylaminomethyl) styrene are added to the reaction flask and the reaction mass is stirred in this mode for another 2 ,5 o'clock.
  • the reaction mass is removed from the glove box, filtered.
  • the solvent is removed on a vacuum rotary evaporator.
  • the residue is suspended in 80 ml of heptane, filtered.
  • the powder is washed with heptane (10 ml), methanol (3x20) ml and dried in a vacuum oven at a temperature of 45 ° C. 2.09 g of a green catalyst are obtained.
  • the yield is 74.4%.
  • the resulting catalyst has the following structural formula:
  • the synthesis is carried out in an argon atmosphere. 2.00 g (2.5 mmol) 1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene (tricyclohexylphosphine) isopentylidene ruthenium dichloride is placed in a 100 ml round bottom flask equipped with a magnetic stirrer, air cooler and oil bath. , 60 ml of dry toluene and 0.95 g (5.0 mmol) of 2- (T, Y-diethylaminomethyl) styrene.
  • the reaction mass is stirred at a temperature of 75 ° C for 2 hours, after which it is removed from the glove box and passed through a 60 A silica gel layer (silica gel mass 10 g, layer thickness 1 cm), the silica gel is washed with a mixture of toluene and dichloromethane in the ratio of dichloromethane: toluene, equal to 2: 1.
  • the solvent is removed on a vacuum rotary evaporator.
  • the residue was suspended in 20 ml of heptane, filtered and washed with heptane (2x10 ml).
  • the obtained green powder is dried in a vacuum oven at a temperature of 45 ° C. 0.94 g of catalyst is obtained.
  • the yield is 59.4%.
  • the resulting catalyst has the following structural formula:
  • SUBSTITUTE SHEET (RULE 26) (glass transition temperature) 120 ° C.
  • the synthesis is carried out in an argon atmosphere. 2.00 g (2.5 mmol) of 1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene) are placed in a 100 ml round bottom flask equipped with a magnetic stirrer, air cooler and oil bath.
  • the solvent is removed on a vacuum rotary evaporator.
  • the residue was suspended in 20 ml of heptane, filtered and washed with heptane (2x 10 ml).
  • the obtained green powder is dried in a vacuum oven at a temperature of 45 ° C. 0.86 g of catalyst is obtained.
  • the yield is 53.8%.
  • the resulting catalyst has the following structural formula:
  • SUBSTITUTE SHEET (RULE 26) aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C. A solid, odorless, transparent sample was obtained. Tg (glass transition temperature) 133 ° C.
  • the synthesis is carried out in an argon atmosphere. 0.50 g (0.63 mmol) of 1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene) are placed in a 25 ml round bottom flask equipped with a magnetic stirrer, air cooler and oil bath.
  • SUBSTITUTE SHEET (RULE 26) aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C. A solid, odorless, transparent sample was obtained. Tg (glass transition temperature) 149 ° C.
  • the synthesis is carried out in an argon atmosphere.
  • 0.30 g (0.43 mmol) of the third-generation Grubbs catalyst ((1, 3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene) (bis) is dissolved in a 25 ml round bottom flask equipped with a magnetic stirrer -pyridine) isopentylidene ruthenium dichloride) in 10 ml of dry toluene, after which 273 mg (1, 1 mmol) of o- (N-methyl- ⁇ -phenylaminomethyl) styrene are added to the reaction flask.
  • the third-generation Grubbs catalyst ((1, 3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene) (bis) is dissolved in a 25 ml round bottom flask equipped with a magnetic stirrer -pyridine) isopentylidene ruthenium dichloride
  • the reaction mixture is stirred for 2 hours at a temperature of 40 ° C and taken out of the glove box.
  • the solvent is removed on a vacuum rotary evaporator.
  • the residue is suspended in 15 ml of hexane, filtered, washed with hexane (10 ml), methanol (3x10 ml), dried in a vacuum oven at a temperature of 45 ° C. Obtain 0.1 1 g of a green catalyst. The yield is 37.9%.
  • the resulting catalyst has the following structural formula:
  • SUBSTITUTE SHEET (RULE 26) 25 ° C.
  • the mixture is heated in aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C.
  • a solid, odorless, transparent sample was obtained.
  • Tg glass transition temperature
  • the synthesis is carried out in an argon atmosphere. 0.50 g (0.63 mmol) 1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene) (tricyclohexylphosphine) is dissolved in a 25 ml round bottom flask equipped with a magnetic stirrer.
  • the resulting catalyst has the following structural formula:
  • SUBSTITUTE SHEET (RULE 26) is 80,000: 1) at 25 ° C. The mixture is heated in aluminum form at 60 ° C for 15 minutes and another 15 minutes at 180 ° C. A solid, odorless, transparent sample was obtained. Tg (glass transition temperature) 152 ° C.
  • the synthesis is carried out in an argon atmosphere. 0.50 g (0.63 mmol) 1, 3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene) (tricyclohexylphosphine) is dissolved in a 25 ml round bottom flask equipped with a magnetic stirrer.
  • the resulting catalyst has the following structural formula:

Abstract

L'invention concerne la chimie métallo-organique et notamment de nouveaux complexes de ruthénium qui sont utilisés en tant que catalyseurs pour la polymérisation du dicyclopentadiène. L'invention décrit des catalyseurs qui se présentent comme des composé complexe de ruthénium possédant en tant que ligands le 1,3-bis-(2,6-diméthylphényl )-2-imidazolidinylidène ou le 1,3-bis-(2,4,6-diméthylphényl )-2-imidazolidinylidène, deux atomes de chlore et un benzylidène ortho-substitué. Le substituant dans le ligand de benzylidène est un groupe méthyle amino-substitué dans lequel on utilise en tant qu'amine des groupes dialkylamino-, di(2-hydroxyéthyle) amino- et alkylphénylamino, ainsi que des amines cycliques, en particulier la pipéridine et la morpholine. Le substituant contenant une amine est en outre coordonné à un atome de ruthénium et forme un cycle chélateur à six groupes. L'invention décrit un procédé de production de polydicyclopentadiène qui comprend la polymérisation de dicyclopentadiène en présence des catalyseurs de l'invention. Le résultat technique consiste en une réduction de la consommation de catalyseur à l'unité, ce qui permet de réduire le prix du polydicyclopentadiène et offre la possibilité de commander le moment de début du processus de polymérisation.
PCT/RU2011/000364 2010-05-27 2011-05-26 Catalyseur à base de ruthénium de la polymérisation par métathèse de dicylcopentadiène (et variantes) et procédé de production de polycylcopentadiène (et variantes) WO2011149388A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2462308C1 (ru) * 2011-10-04 2012-09-27 Общество с ограниченной ответственностью "Объединенный центр исследований и разработок" Катализатор полимеризации дициклопентадиена и способ его получения
WO2015115937A1 (fr) * 2014-01-29 2015-08-06 Открытое акционерное общество "Нефтяная компания "Роснефть" Catalyseur de polymérisation par métathèse de dicyclopentadiène sous forme de complexe de ruthénium, et procédé de fabrication
WO2015115939A1 (fr) * 2014-01-29 2015-08-06 Открытое акционерное общество "Нефтяная компания "Роснефть" Catalyseur de polymérisation par métathèse de dicyclopentadiène et procédé de production

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6111121A (en) * 1995-08-03 2000-08-29 California Institute Of Technology High metathesis activity ruthenium and osmium metal carbene complexes
RU2168518C2 (ru) * 1994-12-23 2001-06-10 Циба Спешиалти Чемикалс Холдинг Инк. Состав, способный к полимеризации
US20050261451A1 (en) * 2004-03-29 2005-11-24 California Institute Of Technology Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand
EP1757613A1 (fr) * 2005-08-22 2007-02-28 Viacatt N.V. Complexes en métal multi coordonné pour l'usage dans des réactions de metathesis
RU2375379C1 (ru) * 2008-05-22 2009-12-10 Общество с ограниченной ответственностью "Объединенный центр исследований и разработок" Катализатор метатезисной полимеризации дициклопентадиена, способ его получения (варианты) и способ его полимеризации
RU2377257C1 (ru) * 2008-07-31 2009-12-27 Общество с ограниченной ответственностью "Объединенный центр исследований и разработок" Способ получения катализатора метатезисной полимеризации дициклопентадиена

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2168518C2 (ru) * 1994-12-23 2001-06-10 Циба Спешиалти Чемикалс Холдинг Инк. Состав, способный к полимеризации
US6111121A (en) * 1995-08-03 2000-08-29 California Institute Of Technology High metathesis activity ruthenium and osmium metal carbene complexes
US20050261451A1 (en) * 2004-03-29 2005-11-24 California Institute Of Technology Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand
EP1757613A1 (fr) * 2005-08-22 2007-02-28 Viacatt N.V. Complexes en métal multi coordonné pour l'usage dans des réactions de metathesis
RU2375379C1 (ru) * 2008-05-22 2009-12-10 Общество с ограниченной ответственностью "Объединенный центр исследований и разработок" Катализатор метатезисной полимеризации дициклопентадиена, способ его получения (варианты) и способ его полимеризации
RU2377257C1 (ru) * 2008-07-31 2009-12-27 Общество с ограниченной ответственностью "Объединенный центр исследований и разработок" Способ получения катализатора метатезисной полимеризации дициклопентадиена

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2462308C1 (ru) * 2011-10-04 2012-09-27 Общество с ограниченной ответственностью "Объединенный центр исследований и разработок" Катализатор полимеризации дициклопентадиена и способ его получения
WO2015115937A1 (fr) * 2014-01-29 2015-08-06 Открытое акционерное общество "Нефтяная компания "Роснефть" Catalyseur de polymérisation par métathèse de dicyclopentadiène sous forme de complexe de ruthénium, et procédé de fabrication
WO2015115939A1 (fr) * 2014-01-29 2015-08-06 Открытое акционерное общество "Нефтяная компания "Роснефть" Catalyseur de polymérisation par métathèse de dicyclopentadiène et procédé de production

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